Apparatus for fluid analysis



April 21, 1959 M. W. GREENE ET AL APPARATUS FOR FLUID ANALYSIS 2 Sheets-Sheet A1 Filed Jan. 6, 1955 Carbon Dioxide 0e fermi/:offen m 6 G 4 Z oo NOU *cvuxvl /Nl/NTORS Memo/V5 W, GRM/v5 .w .m we H N @a @non T E WWHT @wm HE TWH, C 0 K L m, R m H H2 He .5 5 ridge Unbq/ance Apri 2l, 1959' M. w. GREENE ET AL 2,882,719

APPARATUS FOR FLUID ANALYSIS 2 Sheets-Sheet 2 Filed Jan. 6, 1955 m-iiiiiiii V -L/CZ I II i lLJ Amplifier /NVENToQa Nin/.BONE w. GREENE Lou/5 THAYE/ BY THE/? HTTONEYS.

Hfs/mls, K/ECH, Fos TE le@ Herm/5' United States APPARATUS FOR FLUID ANALYSIS The present invention relates to apparatus for the lanalysis of iluids.

It has been known for many years that gas mixtures can be satisfactorily analyzed by measuring the thermal conductivity of such mixtures. In many of these prior procedures, the amount of heat conducted away from a hot electrical element in an unknown gas mixture is compared with the amount of heat conducted away from a second hot electrical element in a known gas or gas mixture, and, by virtue of this comparison, the analysis of the unknown gas mixture is made. In general, the amount of heat conducted from each element in a gas mixture in this type of measurement is measured utilizing the change in resistance of the two elements by virtue of the change in temperature. These changes in' resistance are, in turn, measured by means of a common Wheatstone bridge type electrical circuit.

As nearly as can be determined, all of the prior procedures of'this type rely principally upon the conduction ,as opposed to the removal of heat away from the heated element by means of thermal convection. It is customary to employ various specialized constructions in such gas analysis apparatus in order to prevent the presence of yconvection currents around the heated elements because transfer of heat by convection has been considered undesirable. Such transfer of heat in this manner is generally considered in the -art to prevent accurate heat conductivity measurement. However, in prior art devices of the class broadly described above, both conduction and convection of heat away from such heating elements have occurred, and, invariably, eiorts have been made to balance out the eiect of convection currents by means of special circuits and cell constructions.

The present invention differs from these prior devices in that it is predicated upon the discovery that the removal of heat lby convection currents provides a very ecient and accurate means for determining the composition of most uid mixtures. It is a broad object of lthe instant invention to teach a method utilizing such convection currents in order to determine the composition of a fluid mixture. A further object of the invenvtion is to provide new apparatus which can be used to carry out the instant invention. Other objects of the present disclosure and many advantages of it will be apparent from the remainder of this speciiication and vthe appended claims.

bridge, so as to indicate the composition of the uid .mixture The heat required in such apparatus in order to give rise to the thermal convection necessary may' atcnt O either be supplied by these resistance elements, or by means of various external heating means, as will be more fully described. The invention may also be briey summarized as involving a method in which a fluid is heated adjacent a iirst electrical resistance element and is caused to ow by virtue of the heat so as to conduct heat from adjacent the rst of these elements upwards to a second electrical resistance element, and in which the temperature diierential between the two heating elements is determined in order that the composition of the fluid mixture may be deduced. The invention is, of course, more precisely summarized by the appended claims forming a part of this speciiication. Further details of it will be apparent from the remainder of this description, the claims, and the accompanying drawings, in which:

Fig. l illustrates an isometric, partially sectional view of a new `apparatus of the invention;

Fig. 2 diagrammatically illustrates a modified apparatus of the invention;

Fig. 3 diagrammatically illustrates a second modified apparatus of the invention;

Fig. 4 diagrammatically illustrates a third modified apparatus of the invention;

Fig. 5 shows an electrical measuring circuit used with any of the apparatus falling within the scope of the disclosure;

Fig. 6 shows a second electrical measuring circuit utilized with the invention;

Figs. 7 and 8 are analysis curves used with the invention;

Fig. 9 diagrammatically illustrates a fourth modiied apparatus of the invention;

Fig. 10 diagrammatically illustrates part of a fth modied apparatus of the invention; and

Fig. 11 shows an electrical measuring circuit which may also be employed with any of the apparatus herein disclosed.

For convenience, like numerals are used to designate like parts in all gures of the drawings.

A prime advantage of the instant invention lies in the fact that individual iluids which differ slightly in their heat conduction coefhcients may diier widely in their convection coefficients. Furthermore, some fluids commonly encountered in mixtures have nearly identical convection coeicients, making possible the determination of a component fluid which has a different convection coeicient in a multicomponent uid mixture. For example, oxygen, nitrogen, 4carbon monoxide, and water vapor have approximately the same vconvection coecients, while that of carbon dioxide is approximately twice as great. Inasmuch as the convection coeicients for various iluids vary differently with temperature, it is possible to employ the presently described method at an optimum temperature for any given mixture at which the convection coefficients of the background fluids are most nearly equal. For these reasons, analyses may be made with the present invention that could not be made satisfactorily with the prior apparatus for measuring heat conductivity. The present invention may also be used together with heat conductivity or other measurements in order to obtain a composite analysis of multicomponent gas or liquid systems.

These convection coefficients referred to above can be calculated approximately from the formula where Cp is the isobaric heat capacity per unit weight, d is the density of the uid, and v is the coefficient of viscosity of the uid. This formula can be derived from a consideration of the forces tending to move a unit volume of iluid in proximity to a heated vertical surthe bushing 19 in a common junction.

3 face. When the apparatus .is operated at elevated temperatures, the coeicients calculated by the above procedure no longer apply; however, the measurements obtained permit measurement of iluid'composition by the general jprocedure herein described.

The present invention is .of particular applicability for the 'analysis rof respiratory products or :the analysis of products `of combustion inasmuch as the convection coefiicient for carbon dioxide yis Vconsiderably dilierent from that of :either nitrogen Aor oxygen. The herein described ;method and :apparatus are relatively insensitive to the presence of large :amounts of water vapor such as areencountered .in thehuman breath. Because allof the usual components .of combustion products, .except carbon dioxide, have approximately the `same convection coeicients, .the herein-described process and .apparatus `are effective vfor .the analysis `of gases of .this type.

Perhaps the invention will 'be ybest understood ifreference is made to the'devices shown in the accompanying drawings. In Fig. 1 there is shown a device -used in carrying out the method of 'the present invention consisting of a yU-shaped center block 11 capped on .op-

posed ends by end caps 12 land at the top by means of a lid .13. Within one wall of the center block 11 there are positioned tapped inlet yand outlet openings 1S and 16 respectively leading to a center cavity 27. Within the rlid 13 there are positioned two insulating bushings 18 and 19 carrying at ltheir lower extremities electrical heating rods 21 and 22 which are joined `beneath This junction is connected externally of the device 'by a wire lead 23 projecting Y"through the bushing 19; the other ends of the rods are connected externally of the device by means of wire leads v24 and 25 projecting through the bushing 18. Both the heating rods 21and 22 have 'approximately the same'resistance and are lpositioned parallel to one another. Within the center block V11 these heater rods lare segregated from the cavity 27 by means of a porous screen '28 resting upon shoulders 29 within the center block 11 adjacent the lid 13. This screen is preferably formed of a porous gas-permeable material such as, for example, porous carbon or sintered ceramic frit or the like. The ends of the screen 28 vpreferably contact the oaps 12, eiectively sealing the heating rods 21 and 22 from the balance of the cavity 27.

An appropriate electrical measuring circuit for use with the apparatus illustrated in Fig. 1 is shown in Fig. as consisting of -an electrical lead a connected to :a resistor R1, which is Iconnected -to a second resistor R2, fastened to an Velectricallead c. A battery B is connected across these resistors, 'and ian electrical lead `b containing a galvanometer G 'is connected to the junction between the resistors R1 and R2, as indicated.

In using .the device shown lin Fig. 1, the leads a, b and `ciare connected to the leads 24, 23 and '25. As this occurs, current ows from the battery B, heating the rods 21 fand 22. Anunknown gas or fgas mixture'or liquid `or liquid mixture is then 'passed through the cavity 27 by means of the inlet V15 an'd the outlet 16. A small portion of this fluid diffuses through the screen 28 finto contact with :the heating `rods 21 and 22. At the "lower of these rods, the fluid is heated by contactand thus is caused to ow upward -past the second rod. The ydifference in the `temperatures of these rods caused lby this duid how is measured ."by means of the galvanometer G, which may, if desired, :be calibrated to read the convection coeicient lof thefuid within the 'cavity 27 directly. It will be realized that this type of measuring circuit is that commonly known as a Wheatstone bridge circuit. Various conventional modifications can be made with this circuit; thus a sliding bridge arrangementcan be substituted for the galvanometer G, and other current 4sources besides a battery can be used.

In using the device, fluid from around the heating rods 21 and 22 diiuses out .through the screen 28 Vat the same rate lat which nid diffuses in through the screen 28 into contact with these rods. A screen of the type illustrated is normally employed in order to prevent ow, other than that due to thermal convection, in the vicinity of the resistance elements. It will be realized that such screens may be dispensed with when the design of any specific construction is such lthat there is no extraneous ow past the heating elements. Thus, such screens may be completely dispensed with when a given quantity of fluid is held immobile within an analysis apparatus.

The two heating rods shown in Fig. 1 can be satisfactorily replaced as shown in Fig. `2 by two flatly disposed heating coils 31 and 32 .connected to terminal leads 24 and 25 and |a center lead 23. The use of heating coils of this type permits greater heating action `than could normally .be .obtained with `small rods of the type illustrated in Fig. 1, With '-both of the heater constructions shown Vin Figs. 1 and 2, .the heating-elements must be positioned oneabove the other.

It is also possible to replace the heating `elements 21 .and 22 shown vin Fig. l'by resistance rods 61 and 62 as is -shown in Fig. 3 of the drawing connected by means lof appropriate leads .23, 24 and2`5 as described above into a Wheatstone'hridge `type .of circuit. `Rods of thiscategory must be placed in position parallel to the direction of gravity in order .that 'the convection of heat upward can occur rom 'the bottom heating element 62 to Vthe Vtop one 61. This can be achieved by reconstructing the construction `shown in Fig. 1 in a vertical direction if desired. Other requivalent Ymeans such as resistance coils can 'be used instead of the rods 61 and 62.

A number 'of other devices can be -used withinthe scope of the invention vin 'order to satisfactorily determine the convection coeflcient of fluid mixtures. One such device is 'disclosed 'and claimed in the copending application of Ray I. Wilson, Serial No. 380,303, tiled September 15, 1953, entitled Gas Analysis Cell, `and is :shown in'Fig. 4 'of the drawings herein as consisting of a horizontally disposed ilow tube 71whic`h is designed lto carry a .stream of huid and has 'on opposed sides openings '72 and r73 leading 'to'side passages 74 and 75, repectively, these passages being connected to an analysis tube 76 around which there are disposed windings 77 and 78 in the form of coils which are adapted to be used to measure a convection coe'icientzin substantially the manner *described above. In'utilizing this construction, uid is passed through the dow tube 71 anda `small amount of this iiuid diffuses through the openings'72 and 73 down into the analysis ytube 76 where,`by virtue of the fact'that heated fluids tend to n'se, convectioncurrents are lset up as indicated above. The resistance 'windings 77 and 78 vdisposed around the analysis'tube 76 are connected to a .conventional Wheatstone bridge construction,v as shown in Fig. .5,5by means of leads 23,24 and 25, in the same manner in which the resistance elements indicatedin Fig. 1 of the drawings were similarly connected to a bridge.

The construction shown in Fig. 9 of the drawings .is 'essentially similar to that 'illustrated inFig. 4, except for the inclusionwithin this construction of a heating jacket '80 'disposed about 'the analysis tube 76. This jacket is provided with a conventional inlet 81 andan outlet -82 so that uid may be circulated withinit in ordertoeither heat or cool the contents of the `.analysis tube76. The use of such means .for altering 'the 'temperature of the contents of the analysis tubeis frequently desirable when the apparatus is employed with uids 'at either extremely high or low temperatures. `In Fig. 10 o'f the drawings, anotherconstruction which is related .to Fig. 4 of Ithe drawings is shown. Here there is `illustrated an anlysis tube 76 as employed in Fig. 4, around'which there is disposed a housing`84 containing on its inner surface an electrical heating Velement .85 connected in the exterior of the 'housing vS21 by means of leads 86. Preferably, the

interior of the housing 84 isY formed having a lreiiective. surface. v '1 The operation of the constructions illustrated in Figs. 9 and 10 of the drawings is essentially identicalrwith the operation of the construction shown in Fig. 4. These two figures are employed, however, to'illustrate the fact that with the present invention it is possible to separate the heating used to give rise to convection currents in carrying out the method of the present invention and the means employed to determine the presence of a temperature differential. Within the constructions Figs. 9 and 10, the heat necessary to give rise to the convection currents used is supplied either by a tluid flowing through the heating jacket 80 or by means of the electrical-heating element 85. The temperature diiferential caused by means of such convection currents is measured through the-aid of the windings 77 and 78 substantially as indicated in the preceding discussion.

Those skilled in the art will realize thatvarious equivalent' means of the type broadly pictured in Figs. 1 -through 4, and 9-10 of this application may be employed, and that it is comparatively immaterial with respect to the process of this application whether a screen or a hollow tube is used to segregate the uid being measured from a main flow stream. Further, those skilled in the art will realize that the heating and sensing functions may be separated in constructions of the broad category shown in Fig. 1 in a similar manner in which these functions are separated in the constructions shown in Figs. 9.and 10 of the drawings. A condition which must -be met in all cases is that there is no externally induced ow past the two sensing elements employed which would give rise to unwanted movement of uid past the sensing elements; that is, the iluids analyzed must in all constructions be free to travel by means of convection from one sensing element upward past a second.

In Fig. 6 of the drawings there is shown an electrical circuit for a device which can be used to compare the convection coeicients of two iiuids. This device consists essentially of two cells C1 and C2 of any of the types previously described or indicated in the specication. Both of these cells, however, are preferably of the same construction. Each of them contains resistances R1, R1', R2 and R2' of the type previously described. These resistances are connected at their extremities by means of an appropriate battery B so as to be in parallel. Their midpoints are connected as shown with a galvanometer G which may be calibrated to read directly any changes in resistance within either of the cells C1 or C2. If desired, a potentiometer can be substituted for the calibrated galvanometer. If it is desired to employ a balanced bridge method of detection, it is advantageous to interchange the battery and galvanometer leads. It is to be understood that this type of circuit broadly is known to the art. In using the device shown in Fig. 6, a known gas or liquid is introduced into one of the cells, say cell C2 and an unknown gas or liquid is introduced into the cell C1. The diierence in the convection coeiiicients of the two gases `or liquids is readily apparent by the change in the reading of the galvanometer G. With an arrangement of this type a iirst order compensation for changes in temperature, power supply voltage, barometric pressure, etc., is `automatically obtained.

In Fig. 1l of the drawings, another electrical circuit is shown for a device which can be used to compare the convection coefficients of two diierent uids. This construction consists essentially of two cells C1 and C2 of any of the types previously described or indicated in this specification. Both of the cells are, of course, preferably of the same construction, and contain resistances R1, R2, R1', and R2 of the type described connected at their extremities as shown to an appropriate battery B so as to be parallel with this battery. The junction of the resistances R1 and R2 is connected to a sliding resistor R5 and to a variable resistor R4, as indicated, these latter two resistors being parallel with one another so that the terminal junction remote from the c ell C1 is connected through a resistor R6 to a terminal leadv going to the battery B. The resistor R5 is Iconnected as shown to an amplilier, and is adjusted by meansl of a servomotor, as indicated in the drawings, so that any variation in the voltage drop across the cells C1 and C2 is picked up by means of this amplier causing an adjustment of the resistor R5. Pref.- erably, the servomotor is connected to a recording device so that the difference in convection coe'icients of the fluids within the cells C1 and C2 may be directlydetermined. The amplifier shown isconnected to the junction of the resistances R1 and.R2 in the cell C2 as shown. The. actual operation of the circuit shown in Fig. 11 is considered to be obvious to those skilled in the art, and is essentially similar to the operation of the circuit shown in Fig. 6,

Those skilled in the art will realize that the herein described and disclosed invention is capable of wide modification. Such modiiications are to be considered as p'art'of the instant inventive concept` insofar as they are delined in the appended claims. In order that this disclosure may be complete under the Rules of Practice in the United States Patent Office, the following specific example is given:

In carrying out the process of the invention, an apparatus as illustrated in Fig. 4, utilizing a center tapped platinum winding as heating element, is connected to a Wheatstone-bridge type apparatus, as indicated in Fig. 5, in which the battery supplies a current of milliamps. at 1.8 volts to the platinum windings having a resistance at 20 C. of approximately 5 ohms each. Various gases at 20 C. were passed through the apparatus and the bridge unbalance; that is, the change in resistance of the windings divided by the resistance of one winding, was plotted against the convection coeicient of these gases, as calculated from the formula given earlier in the specification. This plot is shown in Fig. 8 of the drawings. It was then possible to determine by extrapolation the percentage `of an ingredient in a two-component gas mixture by extrapolation between the bridge unbalance for each of the individual components of this mixture and the bridge unbalance of the unknown mixture. This broad method was satisfactorily used `in determining the percentage of carbon dioxide in air-carbon dioxide combustion mixtures by determining the change in bridge unbalance between that normally apparent for nitrogen, oxygen and carbon monoxide, as indicated in Fig. 8, and that for carbon dioxide as indicated in this gure.

For use in determining the carbon dioxide content of respiratory gases, known mixtures of carbon dioxide and air were passed through the apparatus described above and the resistance change divided by the resistance of one of the windings was plotted against the percentage of carbon dioxide in order to obtain the plot shown in Fig. 7. Unknown mixtures of carbon dioxide and air were then passed through the apparatus and from the resistance change divided by the resistance of one arm it was possible to directly `determine the percentage of carbon dioxide in the unknown mixture by the use of this curve.

The procedures indicated in the preceding paragraphs were also carried out using other uids, including water and glycerin mixtures, water and ethyl alcohol mixtures and water and methyl alcohol mixtures. Satisfactory analyses were obtained by this procedure. The results obtained in a-ll curves agreed with results obtained by other methods of analysis.

We claim as our invention:

1. ln an apparatus for measuring the thermal convection coefficient of uid, the combination of: means dening a fluid chamber; diiusion screen means positioned within said chamber, said diffusion screen means separating said chamber into a first zone, and a second zone located above said rst zone; means for introducing a uid into said first zone; a first heating element positioned at asaag'ris 'said-second'zone, a second heating Aelement positioned Jat said "second zone *vertically above l,said first element; and means urespectively responsiveto the temperatures Aof `said elements., `for measuring'the "difference Ain temperature between 'said frrst and second elements.

2. An 'apparatus for measuring the `thermalconvection coeic'ient of a uid, 4which comprises: means dening 'first and second ilud chambers, `said 'second Achamber being'pos'ifioned above said Kfirst chamber; lporous screen means positioned 'between 'said chambers permitting difusion of aiuid from said rst chamber toY said second chamber; means *foradmitting 'and 4withirlrawing fluid to and from said iirst chamber atva'single level; rst andsecond temperature sensitive electrical resistance means positioned one above lthe other within said second chamber; electrical `leadsconnected'to said first and second resistance means; means supplying power to said resistance means; Vand means y'for measuring the difference in the resistances of `said tirst `and second resistance means.

"/Adevice as -defmed rin claim wherein saidresistance means comprise `clinear rods.

-4. A device as defined in claim '.2, wherein said resistance means comprise parallel heating elements.

"ReferencesCited `in'thele of lthis patent UNITED fSTATES PATENTS 2,603,965 Medlock July 22, 1952 2,693,103 .Krupp Nov. 2, 1954 'FOREIGN 'PATENTS 483456011- Germany Mar` 20, 1952 GTI-ER REFERENCES 

